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Free radical bulk and solution polymerizations of a divinyl monomer, ethylene glycol dimethacrylate (EGDMA), in the presence of methyl 2-(bromomethyl)acrylate as an addition–fragmentation chain transfer agent were investigated to synthesize thermally curable hyperbranched polymers by a one-step reaction. Soluble polymers were obtained up to high conversion of EGDMA, and the molecular weight and molecular weight distribution of the polymers increased with increasing EGDMA conversion. 1 H NMR and MALDI-MS analyses revealed that the soluble polymers were obtained after the consumption of a considerable amount of the pendant methacryloyl groups, and one polymer chain contained a number of end groups indicating the formation of hyperbranched polymers. The isolated hyperbranched polymers underwent thermal curing above 110 °C without curing agents, and the polymers having a large number of pendant methacryloyl groups resulted in a significant increase in glass transition temperature, i.e., from around room temperature to above 210 °C.
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Sato et al. (2014) studied this question.
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